CN110446522B

CN110446522B - Medical appliance

Info

Publication number: CN110446522B
Application number: CN201880020081.8A
Authority: CN
Inventors: 大岩智哉
Original assignee: Terumo Corp
Current assignee: Terumo Corp
Priority date: 2017-03-30
Filing date: 2018-03-26
Publication date: 2022-02-18
Anticipated expiration: 2038-03-26
Also published as: EP3603729A4; WO2018181184A1; US11471569B2; CN110446522A; JP6994499B2; EP3603729A1; EP3603729B1; JPWO2018181184A1; US20200023101A1

Abstract

The invention provides a medical device which has high visibility on a nonwoven fabric of green, blue or the like, has excellent visibility with other medical devices having green, blue or the like, and has high adhesion and strength of a coating layer. The medical device of the present invention includes an elongated body, and a resin layer covering at least a proximal end portion of the elongated body, the resin layer including a first layer containing a first fluororesin, an organic pigment, and titanium oxide, and a second layer formed on the first layer and containing a second fluororesin.

Description

Medical appliance

Technical Field

The present invention relates to a medical device.

Background

A guidewire is a medical instrument for guiding a catheter used in Percutaneous Coronary Angioplasty (PTCA) for treating a stenosis in a Coronary artery of a heart, examination of cardiac angiography, or the like. In percutaneous coronary angioplasty, a guide wire is inserted together with a balloon catheter into the vicinity of a stenosis portion of a coronary artery, which is a target site, in a state of protruding from the distal end of the balloon catheter. At the stenosis, only a thin guidewire is first passed through and expanded to open the stenosis while guiding the balloon catheter.

In order to improve the sliding property, the guide wire is coated with a resin layer such as a fluororesin around a core member such as an alloy to facilitate the movement in the blood vessel and the passage through a lesion or the like and to reduce the resistance against the inner wall of the catheter.

As described above, medical instruments such as catheters and guide wires to be inserted into body lumens and tissues such as airways, trachea, digestive tract, urethra and blood vessels are required to have operability to be reliably inserted into a target site without damaging the tissues. Further, in order to avoid damaging the mucous membrane by friction or causing inflammation while being left in the tissue, it is required to exhibit excellent slidability.

On the other hand, since the medical device inserted into a biological lumen or tissue has a small diameter, it is sometimes difficult to visually confirm the medical device immediately in an operating room. Therefore, in jp 2015-100664 a, the resin layer contains a green inorganic pigment such as chromium oxide or cobalt green to color the guide wire, thereby improving the visibility of the guide wire.

Disclosure of Invention

In an operating room where percutaneous coronary angioplasty or the like is performed, a surgical drape, an instrument table cover, a nonwoven fabric such as a gown, or the like is used. These nonwoven fabrics are mostly green and blue in color. If the medical device and these nonwoven fabrics have the same color tone, the medical device and the background color become the same, and it may be difficult for a doctor to visually confirm the medical device immediately. Therefore, the guide wire is required to have various colors not only for the above-described green and blue colors.

In addition, in percutaneous coronary angioplasty, a plurality of guide wires are sometimes used simultaneously depending on the kind of lesion, flexibility, and the like. In an operation in which a plurality of medical instruments are used simultaneously as described above, it is desirable that a physician be able to identify each medical instrument at the hand portion. A method is known in which a marker is provided near a proximal end portion of a guide wire to identify each guide wire. However, since the guide wire is long, the physician needs to perform an operation of separating the hand portion from the proximal end portion of the guide wire and checking the mark provided at the proximal end portion of the guide wire, which requires a lot of time and effort for the physician. Therefore, the guide wire is required to have various colors in a range including the hand portion of the physician so that each medical instrument can be recognized at the hand portion.

In order to improve visibility and recognizability of the medical instrument by the doctor, it is preferable that the medical instrument is colored in a color having high visibility and recognizability with respect to green and blue, such as red. For example, consider the following method: in the guide wire, a coating layer including a fluororesin layer containing a red organic pigment is provided on the outer surface of a core material (elongated body) of the guide wire, thereby coloring the guide wire. The fluororesin layer on the outer surface of the core material (elongated body) of the guide wire is generally formed by coating a coating liquid in which a fluororesin is dispersed in a solvent on the core material and then firing the coating liquid.

However, since the firing for forming the fluororesin layer on the outer surface of the core of the guide wire is generally performed at a high temperature, the organic pigment is discolored, and the color developability of the resin layer may be impaired. In addition, when the coating layer contains a large amount of the organic pigment relative to the fluororesin, it is also necessary to blend a large amount of the dispersant for dispersing the organic pigment. When a large amount of the dispersant is blended, the adhesion between the fluororesin layer and the core material and between the fluororesin layer and the other resin layers to be laminated is impaired, and the coating layer may be easily peeled off.

The present invention has been made to solve the above problems, and an object thereof is to provide a medical device having high visibility to a nonwoven fabric of a color such as green or blue, excellent visibility to another medical device having a color such as green or blue, and high adhesion and strength of a coating layer.

The medical device of the present invention includes an elongated body, and a resin layer covering at least a proximal end portion of the elongated body, the resin layer including a first layer containing a first fluororesin, an organic pigment, and titanium oxide, and a second layer formed on the first layer and containing a second fluororesin.

Drawings

Fig. 1 is a partial longitudinal sectional view showing the guide wire 100 (a sectional view in the axial direction of the guide wire 100).

Fig. 2 is an enlarged cross-sectional view of a region [ a ] surrounded by a single-dot chain line in fig. 1.

Detailed Description

One embodiment of the present invention is a medical device including an elongated body, and a resin layer covering at least a proximal end portion of the elongated body, the resin layer including a first layer containing a first fluororesin, an organic pigment, and titanium oxide, and a second layer formed on the first layer and containing a second fluororesin.

According to the above embodiment, by forming the resin layer (first layer) on the elongated body by using the organic pigment and the titanium oxide at the same time, the heat resistance of the resin layer (first layer) is improved due to the high heat resistance of the titanium oxide, and discoloration of the organic pigment due to firing is suppressed. Even if the organic pigment is discolored more or less, the titanium oxide present in the vicinity of the organic pigment is white, and therefore the brightness of the color is maintained high. Therefore, a coating layer having good color developability of the resin layer (first layer), high visibility to a nonwoven fabric having a color of green, blue or the like, and excellent visibility to a medical instrument having a color of green, blue or the like can be obtained.

Further, by using the organic pigment and the titanium oxide together, the amount of the organic pigment blended in the resin layer (first layer) exerts at least good color developability. Thus, a small amount of dispersant required for dispersing the organic pigment as well as the titanium oxide may or may not be necessary. Therefore, the adhesion between the resin layer (first layer) and the core material or between another resin layer (for example, a second layer) laminated on the first layer is not impaired by the dispersant, and the adhesion of the coating layer is improved. Further, since the mechanical strength of the resin layer is improved by blending titanium oxide as an inorganic filler, the strength of the coating layer can be improved.

The medical device having such a coating layer has high visibility on a nonwoven fabric having a color of green, blue or the like, has excellent visibility with other medical devices having a color of green, blue or the like, and has high adhesion and strength of the coating layer.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

In the present specification, "X to Y" indicating a range includes X and Y, and means "X or more and Y or less". In the present specification, unless otherwise specified, the operation and the measurement of physical properties and the like are performed under the conditions of room temperature (20 ℃ or higher and 25 ℃ or lower)/relative humidity of 40% RH or higher and 50% RH or lower.

The medical device of the present embodiment is, for example, a medical device to be inserted into a living body for use, and specifically, catheters to be inserted or indwelling in a blood vessel, such as an indwelling needle, an IVH catheter, a thermal dilution catheter, an angiographic catheter, a vasodilator (for example, PTCA catheter), a dilator, or an introducer, or a guide wire or a stylet (stylet) for these catheters; catheters inserted or retained in digestive organs orally or nasally, such as gastric tube catheters, feeding catheters, and tube-fed Edible (ED) tubes; catheters inserted or retained in the airway or trachea through the mouth or the nose, such as an oxygen catheter, an oxygen cannula, a tube for an endotracheal tube, a tube tip (cuff), a tube for a tracheotomy tube, a tube tip, and an endotracheal tube; catheters inserted or retained in the urethra and the ureter, such as urethral catheters, urethral catheterization catheters, catheters with urethral balloon catheters, and balloons; various catheters inserted or indwelling in body cavities, organs, and tissues, such as suction catheters, drainage catheters, and rectal catheters; artificial trachea, artificial bronchus; medical devices for extracorporeal circulation therapy (artificial lung, artificial heart, artificial kidney, etc.), circuits thereof; medical instruments requiring low frictional resistance when a living body is inserted into, slid, or placed in an endoscope for insertion into various vessels; and so on.

Among them, the medical device is preferably a catheter or a guide wire, and particularly preferably a guide wire.

Hereinafter, in fig. 1, a mode in which the medical instrument is a guide wire will be described. The dimensional ratios in the drawings are exaggerated for the purpose of illustration and may be different from the actual ratios.

Fig. 1 is a partial longitudinal sectional view of the guide wire 100 (a sectional view in the axial direction of the guide wire 100).

As shown in fig. 1, the guide wire 100 includes a flexible, elongated core portion (core wire) 110 and a wire material 140 wound in a spiral shape, and includes a first coil portion 130a and a second coil portion 130b arranged to cover at least a distal end portion of the core portion 110. As shown in fig. 1,

resin layers

191, 192, 193, and 194, which will be described later, are provided on the outer surface of the guide wire 100 in this order from the distal end side. The resin layers do not necessarily mean the above-described 4 adjacent patterns, and each resin layer may include another resin layer or an exposed portion including a core wire not including a resin layer. Further, the embodiment of providing 4 kinds of resin layers is not necessarily limited to the above-described embodiment, and at least one kind of resin layer among the

resin layers

191, 192, and 193 may not be included, and, for example, the number of resin layers may be increased such that each layer is formed of 2 or more different resin layers.

In the description of the present specification, the longitudinal direction (the left-right direction in fig. 1) of the core 110 is defined as the axial direction, and is indicated by an arrow a1 in each drawing. In the guide wire 100, the side introduced into the living body (into the blood vessel) is defined as the distal side (distal side, left side in fig. 1), and the opposite end side to the distal side is defined as the proximal side (proximal side, right side in fig. 1). In the present specification, the tip portion refers to a portion including a certain range in the axial direction from the tip (foremost end), and the base portion refers to a portion including a certain range in the axial direction from the base (foremost end). In this case, the proximal end does not necessarily include the proximal end (the most proximal end).

The core 110 is an elongated body having a first core 111 disposed on the tip end side in the axial direction, and a second core 112 disposed on the base end side of the first core 111 and joined to the first core 111. The overall length of the core 110 is not particularly limited, but is preferably about 500 to 5000 mm. In particular, for the core 110 of a guidewire used in percutaneous coronary angioplasty, the overall length is typically 1700 to 3000 mm.

The first core portion 111 includes a flat plate portion 111a disposed on the distal end side, a tapered portion 111b extending from the flat plate portion 111a toward the base end side, and an outer diameter constant portion 111c extending from the tapered portion 111b toward the base end side with a substantially constant outer diameter. The shape of the first core 111 is not limited to the illustrated shape. The first core 111 may be formed in a constant outer shape (constant outer diameter) from the distal end side to the proximal end side, for example. For example, the core 110 may be formed of one continuous member, instead of a plurality of members such as the first core 111 and the second core 112. The width and thickness of the flat plate portion 111a are, for example, about 0.1 to 0.5mm and about 0.01 to 0.1 mm. The outer diameter of the outer diameter constant portion 111c is, for example, about 0.2 to 1 mm.

The material of the first core portion 111 and the second core portion 112 is not particularly limited, and various metal materials such as Ni — Ti alloy, stainless steel such as SUS302, SUS304, SUS303, SUS316L, SUS316J1, SUS316J1L, SUS405, SUS430, SUS434, SUS444, SUS429, and SUS430F, piano wire, cobalt alloy, and super-elastic alloy can be used. Among them, in particular, the constituent material of the first core portion 111 is preferably a Ni — Ti-based alloy, and the constituent material of the second core portion 112 is preferably stainless steel. The constituent material of the second core section 112 may be the same as or different from that of the first core section 111. The first core portion 111 and the second core portion 112 can be joined by a joining portion 113 by a method such as welding, for example.

The first coil portion 130a and the second coil portion 130b (hereinafter, these are collectively referred to as the coil portion 130) are arranged so as to cover the first core portion 111 across a fixed range in the axial direction. The coil portion 130 is formed of a wire material 140 spirally wound in the circumferential direction of the core portion 110, with the core portion 110 (first core portion 111) as the center.

The wire 140 has a substantially cylindrical shape in which an inner cavity capable of accommodating the first core 111 is formed.

The coil portion 130 has an inner diameter and an outer diameter that are substantially constant in the axial direction. The axial length of the coil portion 130 and the outer and inner diameters of the coil portion 130 are not particularly limited, and may be appropriately set according to the product specification of the guide wire 100.

The first coil portion 130 is fixed to the peripheries of the flat plate portion 111a and the tapered portion 111b of the first core portion 111 via the first fixing portion 181 and the second fixing portion 182. The second coil portion 130b is fixed to the periphery of the tapered portion 111b and the outer diameter constant portion 111c of the first core portion 111 via the second fixing portion 182 and the third fixing portion 183. The fixing

portions

181, 182, and 183 may be made of, for example, solder, a brazing material, an adhesive, or the like. The distal end surface of the first fixing portion 181 is preferably rounded as shown in the drawing in consideration of influence on a living body lumen such as a blood vessel. The second fixing portion 182 is located at the tapered portion 111b of the first core portion 111.

The constituent material of the wire 140 forming the coil portion 130 is not particularly limited, and for example, a metal such as stainless steel, a super-elastic alloy, a cobalt-based alloy, gold, platinum, or tungsten, or an alloy containing these metals can be used. The coil portion 130 may be formed of different materials on the distal end side and the proximal end side, for example. For example, the first coil portion 130a may be made of a material (e.g., platinum) having a property of not transmitting X-rays, and the second coil portion 130b may be made of a material (e.g., stainless steel) that is more likely to transmit X-rays than the distal end portion. The coil portion 130 is illustrated as a coil portion in which a wire rod has a circular cross section, but may have an elliptical cross section, a rectangular cross section, or the like.

As shown in fig. 1, resin layers 191 are provided on the outer surfaces of the first coil portion 130a and the second coil portion 130 b. The resin layer 191 can be formed for various purposes, and can be provided for the purpose of improving safety when the guide wire 100 is inserted into a blood vessel or the like, for example. To achieve this, the resin layer 191 is preferably hydrophilic. Examples of the hydrophilic material that can constitute the resin layer 191 include cellulose-based high molecular substances, polyethylene oxide-based high molecular substances, maleic anhydride-based high molecular substances (for example, maleic anhydride copolymers such as methyl vinyl ether-maleic anhydride copolymers), acrylamide-based high molecular substances (for example, block copolymers of polyacrylamide and polyglycidyl methacrylate-dimethylacryloyl (PGMA-DMAA)), water-soluble nylon, polyvinyl alcohol, and polyvinylpyrrolidone. Such hydrophilic materials exert high lubricity by wetting (absorbing water) in most cases. Since the distal end portion of the guide wire is required to have high lubricity, such a hydrophilic material is preferably used. The thickness of the resin layer 191 may be appropriately set according to the purpose, material, etc., and for example, the average thickness when wet is 0.1 to 300 μm.

Further, a resin layer 192 is provided on the outer surface of the first core section 111 on the base end side. The resin layer 192 is made of a material that can reduce friction. Examples of the material capable of reducing friction include polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyesters (PET, PBT, and the like), polyamides, polyimides, polyurethanes, polystyrene, polycarbonate, silicone resins, fluororesins (PTFE, ETFE, and the like), and composite materials thereof. The resin layer 192 may contain a component (for example, an organic pigment) other than the above-described friction reducing material, and may have the same configuration as the resin layer 194 described later, for example. That is, the resin layer 192 may be composed of a first layer containing a first fluororesin, an organic pigment, and titanium oxide, and a second layer formed on the first layer and containing a second fluororesin. With the above structure, the resin layer 192 can be colored.

As shown in fig. 1, a resin layer 193 is provided on the outer surface of the core including the joint 113 of the first core 111 and the second core 112. The resin layer 193 preferably has slidability. Examples of materials that can constitute the resin layer 193 include polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyesters (PET, PBT, and the like), polyamides, polyimides, polyurethanes, polystyrene, polycarbonate, silicone resins, fluororesins (PTFE, ETFE, and the like), and composite materials thereof.

At least a part of the second core portion 112 is covered with the resin layer 194. That is, the resin layer 194 is a resin layer covering at least the proximal end portion of the elongated body. In order to provide visibility and visibility to the medical device, the resin layer 194 is composed of a first layer containing a first fluororesin, an organic pigment, and titanium oxide, and a second layer formed on the first layer and containing a second fluororesin.

The resin layer 194 is preferably provided in a range including the hand edge of the doctor. The region including the hand portion of the physician includes a portion where the guide wire is exposed from the proximal end of the catheter when a general guide catheter (having a length of 800 to 1000mm) is used in percutaneous coronary angioplasty. Specifically, a mode in which the resin layer is provided between the base end of the guide wire and a position 300mm away from the distal end of the guide wire toward the base end side is given. The resin layer 194 is provided between the "position 300mm away from the distal end of the guide wire toward the proximal end side and the base end of the guide wire", and the resin layer 194 may be provided over the entire length between the position 300mm away from the distal end toward the proximal end side and the base end of the guide wire, or may be provided in a part between the position 300mm away from the distal end toward the proximal end side and the base end of the guide wire. The form of providing the resin layer 194 at a portion between the position 300mm away from the distal end toward the proximal end side and the proximal end of the guide wire includes not only the form of providing the resin layer 194 continuously, but also the form of providing the resin layer 194 at a plurality of separate portions.

In the aspect in which the resin layer 194 is "provided between the position 300mm away from the distal end of the guide wire toward the proximal end side and the base end of the guide wire", the resin layer 194 is preferably provided between the position 300mm away from the distal end of the guide wire toward the proximal end side and the position 3500mm away from the distal end of the guide wire toward the proximal end side (aspect 1), more preferably between the position 300mm away from the distal end of the guide wire toward the proximal end side and the position 3000mm away from the distal end of the guide wire toward the proximal end side, and still more preferably between the position 350mm away from the distal end of the guide wire toward the proximal end side and the position 3000mm away from the distal end of the guide wire toward the proximal end side. If the resin layer 194 is provided in the above range, the guide wire has a colored region at the hand portion where the doctor operates the guide wire. Therefore, even if the mark on the proximal end side is not confirmed in the operation in which a plurality of medical instruments are used simultaneously, the doctor can easily identify each medical instrument at the hand portion. In the embodiment in which the resin layer 194 is provided "between the base end of the guide wire and a position 300mm away from the distal end of the guide wire toward the base end side", the resin layer 194 may be provided on the base end side of the guide wire. Specifically, a mode (mode 2) may be mentioned in which the resin layer 194 is provided at least in a part between a position 50mm away from the base end of the guide wire toward the distal end side and the base end of the guide wire. If the resin layer 194 is provided in the above range, the physician can easily recognize the guide wire when replacing the catheter. Either one of the modes 1 and 2 may be used, or both the modes 1 and 2 may be used simultaneously.

As a mode of providing the resin layer 194 at a portion between the position 300mm apart from the distal end toward the proximal end side and the proximal end of the guide wire, for example, when the total length of the guide wire is 1800mm, there may be mentioned (1) a mode of providing the resin layer 194 at least at a portion between a position 400mm apart from the distal end of the guide wire toward the proximal end side and a position 1500mm apart from the distal end of the guide wire toward the proximal end side, and/or (2) a mode of providing the resin layer 194 at least at a portion between a position 1750mm apart from the distal end of the guide wire toward the proximal end side and a position 1790mm apart from the distal end of the guide wire toward the proximal end side. By providing the resin layer 194 at the position of (1), the physician can more easily recognize the guide wire at the hand, and by providing the resin layer 194 at the position of (2), the physician can more easily recognize the guide wire when replacing the catheter.

Fig. 2 is an enlarged cross-sectional view of a region [ a ] surrounded by a single-dot chain line in fig. 1. In fig. 2, the resin layer 194 includes a first layer 151 and a second layer 152. In fig. 2, the second core 112, the first layer 151, and the second layer 152 are arranged in this order. That is, the first layer 151 is disposed on the inner layer (second core portion (elongated body) side) of the second layer 152, and the second layer 152 is disposed on the outermost surface side.

The second layer 152 contains a fluororesin (second fluorine resin). As the insertion operation of the guide wire proceeds, a part of the proximal end side (proximal side) enters the inside of the catheter. By making the second layer contain a fluorine-containing resin, the frictional resistance of the guide wire surface becomes small. As a result, the frictional resistance (sliding resistance) between the guide wire and the inner wall of the catheter is reduced, and the operability of the guide wire in the catheter is improved. Further, by making the second layer contain a fluorine resin, kinking (kinking) and twisting of the guide wire can be prevented when the guide wire is moved/rotated in the catheter.

In fig. 1, the proximal end (the most proximal end) does not have the resin layer 194, because it is not necessary to impart lubricity since the proximal end (the most proximal end) is not inserted into the body. In this way, the base end portion in the phrase "the resin layer covers at least the base end portion of the elongated body" is not limited to the case including the base end, and a certain region on the base end side may be covered with the resin layer.

The total content of the organic pigment and titanium oxide in the second layer is preferably less than 5% by weight (lower limit: 0% by weight), more preferably less than 3% by weight (lower limit: 0% by weight), still more preferably less than 1% by weight (lower limit: 0% by weight), and most preferably 0% by weight, based on the solid content of the second layer. By reducing the total content of the organic pigment and titanium oxide in the second layer, the surface smoothness of the second layer on the outermost surface side, that is, the outermost surface side, is improved, and the second layer can be prevented from peeling off. The content of the organic pigment and the particles other than titanium oxide (for example, other inorganic pigments and organic pigments) contained in the second layer is preferably less than 5% by weight (lower limit: 0% by weight), more preferably less than 3% by weight (lower limit: 0% by weight), still more preferably less than 1% by weight (lower limit: 0% by weight), and most preferably 0% by weight. The solid component is a component other than a solvent that volatilizes when the coating liquid is dried and fired, and examples thereof include a fluororesin, an organic pigment, titanium oxide, a dispersant, a thickener, and the like.

The second layer containing a fluororesin for imparting slidability has very low adhesion to an elongated body such as a core member. Therefore, the first layer is provided between the elongated body and the second layer for the purpose of improving the adhesion between the second layer and the elongated body. That is, a first layer is formed on the elongated body, and a second layer is formed on the first layer.

The phrase "forming a second layer on a first layer" means that the elongated body, the first layer, and the second layer are formed in this order, and does not necessarily mean that the second layer is adjacent to the first layer, and an intermediate layer may be included between the first layer and the second layer. Likewise, the first layer need not be adjacent the body, but may have an intermediate layer between the body and the first layer. However, in order to improve the adhesion of the second layer to the elongated body, it is preferable that the elongated body be adjacent to each of the first layer and the second layer.

The first layer and the second layer may be a single layer or a plurality of layers.

[ resin layer ]

The resin layer 194 includes: a first layer 151 containing a first fluorine resin, an organic pigment, and titanium oxide, and a second layer 152 formed on the first layer and containing a second fluorine resin.

The thickness of the resin layer 194 is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more, from the viewpoint of providing slidability, visibility, and visibility. In consideration of influences on the adhesion of the coating layer and the physical properties of the guide wire, the thickness of the resin layer 194 is preferably 200 μm or less, more preferably 100 μm or less, and further preferably 50 μm or less. Specifically, the thickness of the resin layer 194 is preferably 1 to 200 μm, and more preferably 3 to 50 μm.

(first and second fluorine resins)

The first layer 151 includes a first fluorine resin, and the second layer 152 includes a second fluorine resin.

The first fluororesin and the second fluororesin are not particularly limited, but preferably contain at least one selected from the group consisting of Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (PETFE), and more preferably contain at least one of Polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP), from the viewpoint of imparting slidability to the surface, chemical resistance, antithrombotic property, non-tackiness, and the like. From the viewpoint of melting the first layer and the second layer at a lower temperature, the first fluororesin particularly preferably contains both Polytetrafluoroethylene (PTFE) and a tetrafluoroethylene-hexafluoropropylene copolymer (FEP). In this case, the weight ratio of PTFE to FEP (PTFE: FEP) is preferably 1: 0.1-1: 15, more preferably 1: 1-1: 10, more preferably 1: 1-1: 7. further, it is particularly preferable that the second fluorine resin is Polytetrafluoroethylene (PTFE).

The first fluororesin and the second fluororesin may be of the same kind or of different kinds. The first fluororesin and the second fluororesin may contain a plurality of kinds of fluororesins.

(organic pigment)

In the present invention, the organic pigment has an effect of coloring the first layer to impart visibility and recognizability to the medical device. As the organic pigment, organic pigments having a color of red, yellow, orange or the like are preferably used from the viewpoint of visibility on nonwoven fabrics having a color of green, blue or the like, or visibility with other medical instruments having a color of green, blue or the like.

Examples of the organic pigment exhibiting red, yellow, orange or other colors include water-insoluble azo pigments such as toluidine red, toluidine chestnut, hanza yellow (hanza yellow), benzidine yellow, and pyrazolone red; water-soluble azo pigments such as lisolred (litholred), heliobodol red (helio bordeax), pigment scarlet (pigment scarlet), permanent red 2B (permanent red 2B), and the like; anthraquinone pigments such as dianthraquinone red; quinacridone pigments such as quinacridone red and quinacridone magenta; pyranthrone-based pigments such as pyranthrone red and pyranthrone orange; perylene pigments such as perylene red and perylene scarlet; diketopyrrolopyrrole pigments such as diketopyrrolopyrrole red. That is, in one embodiment of the present invention, the organic pigment includes at least one selected from the group consisting of azo pigments, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, perylene pigments, and diketopyrrolopyrrole pigments. Among them, the organic pigment preferably contains a quinacridone pigment.

When the organic pigment is exemplified by the color index (c.i.) number, examples thereof include c.i. pigment yellow 12, c.i. pigment yellow 13, c.i. pigment yellow 14, c.i. pigment yellow 17, c.i. pigment yellow 20, c.i. pigment yellow 24, c.i. pigment yellow 74, c.i. pigment yellow 83, c.i. pigment yellow 86, c.i. pigment yellow 93, c.i. pigment yellow 109, c.i. pigment yellow 110, c.i. pigment yellow 117, c.i. pigment yellow 120, c.i. pigment yellow 125, c.i. pigment yellow 128, c.i. pigment yellow 129, c.i. pigment yellow 137, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 147, c.i. pigment yellow 148, c.i. pigment yellow 150, c.i. pigment yellow 151, c.i. pigment yellow 153, c.i. pigment yellow 185; c.i. pigment orange 16, c.i. pigment orange 36, c.i. pigment orange 43, c.i. pigment orange 51, c.i. pigment orange 55, c.i. pigment orange 59, c.i. pigment orange 61; c.i. pigment red 9, c.i. pigment red 48, c.i. pigment red 49, c.i. pigment red 52, c.i. pigment red 53, c.i. pigment red 57, c.i. pigment red 97, c.i. pigment red 122, c.i. pigment red 123, c.i. pigment red 149, c.i. pigment red 168, c.i. pigment red 177, c.i. pigment red 180, c.i. pigment red 192, c.i. pigment red 202, c.i. pigment red 206, c.i. pigment red 215, c.i. pigment red 216, c.i. pigment red 217, c.i. pigment red 220, c.i. pigment red 223, c.i. pigment red 224, c.i. pigment red 226, c.i. pigment red 227, c.i. pigment red 228, c.i. pigment red 238, c.i. pigment red 240; c.i. pigment violet 19, c.i. pigment violet 23, c.i. pigment violet 29, c.i. pigment violet 30, c.i. pigment violet 37, c.i. pigment violet 40, c.i. pigment violet 50, and the like. These may be used in 1 kind, or 2 or more kinds may be used in combination.

In the first layer, the content of the organic pigment is preferably 5% by weight or more, more preferably 20% by weight or more, further preferably 30% by weight or more, and particularly preferably 35% by weight or more, relative to the content of the first fluororesin. When the content is within the above range, the color developability of the first layer is good, and the visibility and the recognizability of the medical device are improved. In addition, from the viewpoint of dispersibility of the organic pigment in the first layer and adhesion of the coating layer, the content of the organic pigment in the first layer is preferably 300% by weight or less, more preferably 250% by weight or less, even more preferably 200% by weight or less, and particularly preferably 150% by weight or less, relative to the content of the first fluororesin. Among them, from the viewpoint of further improving the visibility of the medical device and the adhesion of the coating layer, it is preferably 100% by weight or less, and more preferably 95% by weight or less. For the same reason, the content of the organic pigment is preferably 1 to 150% by weight, more preferably 3 to 100% by weight, still more preferably 5 to 50% by weight, and particularly preferably 8 to 40% by weight, based on the solid content of the first layer. Among them, from the viewpoint of further improving the visibility of the medical instrument and the adhesion of the coating layer, it is preferably 8 to 35% by weight, more preferably 8 to 30% by weight, and particularly preferably 8 to 25% by weight.

The organic pigment preferably has an average particle diameter of 50 to 900nm, more preferably 90 to 600nm, from the viewpoint of dispersibility and colorability. The average particle diameter of the organic pigment is a volume-based median diameter measured by a laser diffraction scattering method.

In order to ensure dispersion stability, the organic pigment may be surface-treated by a known technique such as acid treatment, alkali treatment, treatment with a synergist, or treatment with various coupling agents.

The organic pigment may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(titanium oxide)

In the present invention, titanium oxide has an effect of improving the color developability and strength of the first layer. The titanium oxide may be any of rutile type and anatase type, and rutile type is preferable in terms of color rendering properties.

From the viewpoint of dispersibility and dispersion stability, the average particle diameter of the titanium oxide is preferably 50 to 700nm, more preferably 100 to 500nm, and still more preferably 200 to 300 nm. The average particle diameter of titanium oxide is a volume-based median diameter measured by a laser diffraction scattering method.

In the first layer, the content of titanium oxide is preferably 5% by weight or more, more preferably 20% by weight or more, further more preferably 30% by weight or more, and particularly preferably 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight, or 90% by weight or more, relative to the content of the first fluororesin. When the content is within the above range, the color developability of the first layer is improved, and the visibility is improved. Further, a medical device having excellent adhesion and strength between the first layer and the second layer can be obtained. In the first layer, for the same reason, the content of titanium oxide is preferably 400 wt% or less, more preferably 360 wt% or less, with respect to the content of the first fluororesin. For the same reason, the content of titanium oxide is preferably 1 to 150% by weight, more preferably 3 to 100% by weight, still more preferably 5 to 50% by weight, and particularly preferably 8 to 40% by weight, based on the solid content of the first layer.

In the first layer, the content of titanium oxide is preferably 10% by weight or more, more preferably 25% by weight or more, further more preferably 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, and particularly preferably 100% by weight or more, relative to 100% by weight of the content of the organic pigment. When the content is within the above range, the color developability of the first layer is improved, and the visibility is improved. In addition, the adhesion and strength between the first layer and the second layer are improved. Further, from the viewpoint of further improving the brightness of the color of the coating layer, and further improving the visibility and the visibility of the medical device, it is more preferably 110 wt% or more, 120 wt% or more, 130 wt% or more, and 140 wt% or more, and particularly preferably 150 wt% or more, 160 wt% or more, 170 wt% or more, 180 wt% or more, and 185 wt% or more. In the first layer, the content of titanium oxide is preferably 600 wt% or less, more preferably 550 wt% or less, further more preferably 500 wt% or less, and particularly preferably 400 wt% or less, with respect to 100 wt% of the content of the organic pigment, in view of the color developability of the medical device. That is, in one embodiment of the present invention, the content of titanium oxide is preferably 25% by weight or more and 600% by weight or less, and more preferably 100% by weight or more and 400% by weight or less, with respect to 100% by weight of the content of the organic pigment.

(dispersing agent)

In the present invention, the first layer may further contain a dispersant. The inclusion of the dispersant improves the dispersibility of the titanium oxide with respect to the organic pigment and the fluororesin, and further improves the color developability and strength of the first layer.

In one embodiment of the present invention, the first layer further contains a dispersant, and the content of the dispersant is 80% by weight or less with respect to 100% by weight of the total content of the organic pigment and the titanium oxide. Among these, from the viewpoint of adhesion between the first layer and the second layer, the content of the dispersant is preferably 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, or 30% by weight, more preferably 25% by weight or less, still more preferably 20% by weight or less, still more preferably 15% by weight or less, and particularly preferably 12% by weight or less, based on 100% by weight of the total content of the organic pigment and the titanium oxide. On the other hand, from the viewpoint of further improving the color developability and strength of the first layer, the content of the dispersant is preferably 1% by weight or more, more preferably 2% by weight or more, even more preferably 3% by weight or more, and particularly preferably 3.5% by weight or more, relative to 100% by weight of the total content of the organic pigment and the titanium oxide. For the same reason, the content of the dispersant is preferably 0.5 to 30% by weight, more preferably 0.5 to 25% by weight, even more preferably 0.5 to 20% by weight, even more preferably 1 to 15% by weight, and particularly preferably 1.5 to 12% by weight, based on the solid content of the first layer. The third decimal place of the mixing ratio of the dispersant is obtained, and the second decimal place of the mixing ratio is obtained by rounding.

The dispersant is preferably a polymeric dispersant. The polymeric dispersant inhibits aggregation of the organic pigment and titanium oxide by steric hindrance of the main chain or the side chain, and can improve dispersibility of the organic pigment and titanium oxide and realize stabilization. The weight average molecular weight of the polymer constituting the dispersant is preferably 500 to 200,000. The weight average molecular weight of the polymer constituting the dispersant is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (developing solvent: tetrahydrofuran).

As the dispersant, commercially available products can be used. Examples of usable dispersants include DISPERBYK-2000, DISPERBYK-2013, DISPERBYK-2055 (BYK-Chemie), DISPARLON DA-703-50 (manufactured by Kusumoto Chemicals, Ltd.), AJISPER-PB821, AJISPER-PB822, and AJISPER-PB881 (manufactured by Ajinomoto Fine-Technio Co., Inc.).

The dispersant may be used in 1 kind, or 2 or more kinds may be used in combination.

(tackifier)

In addition, in order to further improve dispersion stability of the organic pigment and titanium oxide and to control the coating thickness by adjusting the viscosity of the coating liquid for forming the first layer, it is preferable that the first layer further contains a thickener. Examples of the thickener include polyamide waxes, metal soaps, organoclay minerals, polyethylene oxide compounds, hydrogenated castor oil waxes, and inorganic fine particles such as fine silica powder. From the viewpoint of further improving the stability of the coating liquid, the thickener is more preferably an inorganic fine particle such as a metal soap, an organoclay mineral, an oxidized polyethylene compound, or a fine silica powder, and from the viewpoint of enabling the dispersibility of titanium oxide to be more stabilized, the thickener is more preferably an organoclay mineral.

Examples of the organoclay mineral include clay minerals obtained by organically treating clay minerals such as natural minerals montmorillonite (bentonite) classified into smectite (smectite), chain clay minerals such as hectorite, saponite, layered clay minerals and sepiolite, and fibrous clay minerals such as palygorskite. The organic treatment is generally carried out using an alkyl quaternary ammonium compound, and the dispersibility of the obtained organoclay mineral is improved by making the surface of the clay mineral hydrophobic.

Commercially available tackifiers can be used. Examples of the tackifier that can be used include Bentoni LT, Benaqua 4000 (manufactured by Elementis Specialties), Optigel CK, Optigel LX, GARAMIE 7305 (manufactured by BYK-Chemie), "KUBIS" (registered trademark) -110, "SUMECTON" (registered trademark) SA, "SUMECTON" (registered trademark) SAN, "SUMECTON" (registered trademark) STN (KUMINE INDUSTRIES, LTD.), "S-BEN" (registered trademark) N400, "S-BEN" (registered trademark) NX, "S-BEN" (registered trademark) NZ (HOJUN Co., manufactured by Ltd.), and the like.

The amount of the thickener is appropriately set in consideration of the amounts of the organic pigment and titanium oxide to be mixed, the dispersant to be used, and the like. From the viewpoint of stability of the coating liquid, the thickener is preferably 0.01 to 10 wt%, more preferably 0.10 to 5.00 wt%, and still more preferably 0.20 to 2.00 wt% with respect to the solid content of the first layer. The blending ratio of the thickener is determined to the third decimal place, and is rounded off and determined to the second decimal place.

The tackifier may be used in 1 kind, or 2 or more kinds may be used in combination.

The first layer may contain a binder resin to improve adhesion to the elongated body. The binder resin is not particularly limited, and examples thereof include a polyamideimide resin, an epoxy resin, a polyphenylene sulfide resin, a polyether sulfone resin, a polyether ketone resin, a polyether amide resin, a polysulfone resin, a polyimide resin, and a parylene resin. The binder resin may be used in 1 kind, or 2 or more kinds may be used in combination.

The content of the binder resin in the first layer is preferably 5 to 50 wt%, more preferably 10 to 40 wt% based on the solid content of the first layer, in view of adhesion to the elongated body.

The first layer may also contain particles other than titanium oxide (e.g., a coloring pigment). However, if the content of the particles is too large, the first layer becomes brittle, and the effect of improving the adhesion of the second layer to the elongated body becomes insufficient. Therefore, the content of particles other than titanium oxide is preferably 10 wt% or less (lower limit 0 wt%), and more preferably 5 wt% or less (lower limit 0 wt%).

The content of the first fluororesin in the first layer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the solid content of the first layer, in view of adhesion to the second layer.

The thickness of the first layer is not particularly limited, but is preferably 0.8 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, from the viewpoint of visibility and visibility of the medical instrument. In consideration of the adhesion between the first layer and the layer adjacent to the first layer (for example, the elongated body, the second layer, the intermediate layer adjacent to the first layer, and the like), the thickness of the first layer is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 25 μm or less, and particularly preferably 10 μm or less. The thickness of the first layer is preferably 0.8 to 100 μm, more preferably 1 to 50 μm, still more preferably 1 to 25 μm, and particularly preferably 2 to 10 μm.

The content of the second fluorine resin in the second layer is preferably 75 to 100% by weight, more preferably 85 to 100% by weight, in view of the slidability effect exhibited on the surface of the medical device.

The thickness of the second layer is not particularly limited, but is preferably 0.8 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, from the viewpoint of imparting slidability to the medical device and suppressing discoloration of the first layer due to firing. In consideration of the adhesion between the second layer and a layer adjacent to the second layer (for example, the first layer, an intermediate layer adjacent to the second layer, or the like), the thickness of the second layer is preferably 50 μm or less, more preferably 25 μm or less, and still more preferably 10 μm or less.

In the present specification, the thickness of a layer means that the average value of the thicknesses of 5 arbitrary portions of the portion where the selection target layer exists is taken. Further, the thickness of each layer can be measured from a cross-sectional photograph of the medical device. Specifically, the thickness of the layer can be calculated by taking a cross-sectional photograph of the medical device, subtracting the outer diameter of the elongated body from the outer diameter of the medical device, and taking half of the difference thus obtained. In this case, the thickness is determined to the second decimal place, and the average value is determined to the first decimal place by rounding the second decimal place. The thickness of the first layer can be calculated by subtracting the thickness of the second layer from the thickness of the entire resin layer.

Other additives may be added to each layer constituting the resin layer as needed. Examples of such additives include organic pigments, inorganic pigments, dispersion stabilizers, leveling agents, antifoaming agents, chelating agents, antioxidants, and plasticizers.

[ production method ]

The method for producing the medical device of the present embodiment is not particularly limited, and a production method including: coating a coating liquid (hereinafter referred to as a first layer-forming coating liquid) containing a first fluororesin, an organic pigment, and titanium oxide on at least a proximal end portion of the elongated body to form a first coating film; and a step of forming a second coating film by applying a coating liquid containing a second fluorine resin (hereinafter referred to as a second layer-forming coating liquid) onto the first coating film, and then firing the second coating film at a temperature not lower than the melting points of the first fluorine resin and the second fluorine resin.

First, a coating liquid for forming a first layer is prepared. The first layer-forming coating liquid contains a first fluororesin, an organic pigment, titanium oxide, a binder resin, and a dispersant. The coating liquid preferably contains a solvent as a dispersion medium for dispersing them. As the solvent, water, an organic solvent, and a mixed solvent of water and an organic solvent can be used.

Examples of the organic solvent include aromatic solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and cellosolve organic solvents such as methyl cellosolve and ethyl cellosolve. These organic solvents may be used in 1 kind, or 2 or more kinds may be used in combination.

The amount of the organic solvent to be added is appropriately set in consideration of the viscosity of the coating liquid and the dispersibility of each component, but it is preferable to add the organic solvent to the coating liquid for forming the first layer so as to be 40 to 70 wt%.

The mixing order of the organic solvent and each component is not particularly limited, and any order of addition such as mixing the organic solvent with each component and adding each component to the organic solvent in sequence may be used.

The method for applying the first layer-forming coating liquid to the proximal end portion of the elongated body is not particularly limited. Specific examples thereof include dipping (nipping), dropping, blade coating, spin coating, brush coating, spray coating, roll coating, air knife coating, curtain coating, wire bar coating, gravure coating, screen printing, and the like. The method of applying the first layer-forming coating liquid is preferably dipping (spreading) from the viewpoint of uniform coating on the surface and easy control of the film thickness. The speed of lifting at the time of immersion is appropriately set to a desired film thickness, and is, for example, 5 to 150 mm/sec. The viscosity of the coating liquid is appropriately set so that the desired film thickness is obtained, and is, for example, 5 to 70 pas (25 ℃).

Preferably, the first layer-forming coating liquid is applied to at least the proximal end portion of the elongated body and then dried. The drying temperature is not particularly limited as long as the solvent can be removed, and is preferably 50 to 300 ℃, and more preferably 100 to 200 ℃. The drying time is not particularly limited as long as the solvent can be removed, and is preferably 10 minutes or less, more preferably 5 minutes or less, and still more preferably 60 seconds or less.

Further, the coating-drying step may be repeated.

In the above manner, the first coating film was obtained.

Next, a second layer forming coating liquid is prepared. The second layer-forming coating liquid contains a second fluorine resin. The coating liquid preferably contains a solvent as a dispersion medium for dispersing the second fluorine resin. As the solvent, water, an organic solvent, and a mixed solvent of water and an organic solvent can be used. Examples of the organic solvent include those used in the coating liquid for forming the first layer.

The prepared coating liquid for forming the second layer is applied to the first coating film. The method for applying the coating liquid for forming the second layer to the first coating film is not particularly limited. Specifically, dipping (dipping), dropping, blade coating, spin coating, brush coating, spray coating, roll coating, air knife coating, curtain coating, wire bar coating, gravure coating, screen printing, or the like can be mentioned. The method of applying the second layer-forming coating liquid is preferably dipping (spreading) from the viewpoint of uniform coating on the surface and easy control of the film thickness. The pulling-up speed during dipping is set appropriately so that the film thickness is a desired film thickness, for example, 5 to 150 mm/sec. The viscosity of the coating liquid is appropriately set so that the desired film thickness is obtained, and is, for example, 5 to 70 pas (25 ℃).

The second layer-forming coating liquid is preferably applied to the first coating film and then dried. The drying temperature is not particularly limited as long as the temperature is a temperature at which the solvent can be removed, but is preferably 50 to 300 ℃, and more preferably 100 to 200 ℃. The drying time is not particularly limited as long as the solvent can be removed, but is preferably 10 minutes or less, more preferably 5 minutes or less, and still more preferably 60 seconds or less.

In the above manner, the second coating film was obtained.

Finally, the firing is performed at a temperature not lower than the melting points of the first fluororesin and the second fluororesin. The fluororesin is melted by firing at a temperature not lower than the melting point to form a coating layer.

The firing temperature is not particularly limited as long as it is not lower than the melting point of the first fluororesin and the second fluororesin, but is preferably higher than the higher melting point of the first fluororesin and the second fluororesin by not lower than 20 ℃, more specifically, preferably 300 to 550 ℃, and still more preferably 400 to 550 ℃. The firing time is preferably 30 seconds or more. By setting the time to 30 seconds or more, the fluororesin is appropriately fired, and the adhesion and strength are improved. The upper limit of the firing time is not particularly limited, but is preferably 2 minutes or less, and more preferably 60 seconds or less, from the viewpoint of reduction in production efficiency and coloring (yellowing).

Examples

The effects of the present invention will be described with reference to the following examples and comparative examples. In the examples, the expression "part" or "%" is sometimes used, and unless otherwise specified, it means "part by weight" or "% by weight". In addition, each operation was carried out at room temperature (25 ℃ C.), unless otherwise specified.

(example 1)

(preparation of coating liquid for Forming first layer)

A quinacridone-based organic pigment (C.I. pigment Violet 19 having an average particle diameter of 430nm)32.0g (36.8% by weight based on the solid content), titanium oxide (C.I. pigment white 6, rutile type, average particle diameter of 250nm)8.0g (25% by weight based on the organic pigment and 9.2% by weight based on the solid content), methyl isobutyl ketone (132.0 g) as a solvent, polytetrafluoroethylene (PTFE, average particle diameter of 0.20 μm, melting point 327 ℃ C.), tetrafluoroethylene-hexafluoropropylene copolymer (FEP, average particle diameter of 0.20 μm, melting point 270 ℃ C.) 16.1g, polyphenylene sulfide resin (21.5 g) as a binder resin, DISPERBYK 2055(BYK-Chemie Co., Ltd.) as a dispersant, 3.2g (8% by weight based on the organic pigment and titanium oxide, 3.7% by weight based on the solid content), GARAMITE 7305(BYK-Chemie Co., Ltd.) as a thickener, 0.8% by weight based on the solid content, the mixture was stirred with a ball mill to prepare a first layer-forming coating liquid.

(coating liquid for second layer formation)

A coating liquid for forming a second layer was prepared by mixing 100.0g of polytetrafluoroethylene (PTFE, average particle diameter 0.20 μm, melting point 327 ℃ C.) and 100.0g of water.

(coating)

A bare metal wire (SUS302, diameter 0.340mm) was immersed in the coating liquid for forming the first layer and pulled up at 14 mm/sec. Then, drying was performed at 200 ℃ for 60 seconds using a heater. Subsequently, the substrate was immersed in the coating liquid for forming a second layer and pulled up at 20 mm/sec. Then, drying was performed at 200 ℃ for 60 seconds using a heater. Finally, the resultant was baked at 500 ℃ for 60 seconds to obtain a guide wire.

The thickness of the first layer of the resulting guide wire was 2.0 μm, the thickness of the second layer was 3.0 μm, and the thickness of the resin layer (first layer + second layer) was 5.0 μm.

(example 2)

A guidewire was obtained in the same manner as in example 1, except that the loading of the quinacridone organic pigment was changed to 20.0g (23.0 wt% based on the solid content) and the loading of the titanium oxide was changed to 20.0g (100 wt% based on the organic pigment and 23.0 wt% based on the solid content) in the preparation of the coating liquid for forming the first layer.

(example 3)

A guide wire was obtained in the same manner as in example 1, except that the loading of the quinacridone organic pigment was changed to 16.0g (18.4 wt% based on the solid content) and the loading of the titanium oxide was changed to 24.0g (150 wt% based on the organic pigment and 27.6 wt% based on the solid content) in the preparation of the coating liquid for forming the first layer.

(example 4)

A guide wire was obtained in the same manner as in example 1, except that the loading of the quinacridone organic pigment was changed to 14.0g (16.1% by weight based on the solid content) and the loading of the titanium oxide was changed to 26.0g (186% by weight based on the organic pigment and 29.9% by weight based on the solid content) in the preparation of the coating liquid for forming the first layer.

(example 5)

A guide wire was obtained in the same manner as in example 1, except that the loading of the quinacridone organic pigment was changed to 8.0g (9.2 wt% based on the solid content) and the loading of the titanium oxide was changed to 32.0g (400 wt% based on the organic pigment and 36.8 wt% based on the solid content) in the preparation of the coating liquid for forming the first layer.

Comparative example 1

A guidewire was obtained in the same manner as in example 1, except that titanium oxide was not added to the preparation of the first layer forming coating liquid.

Comparative example 2

A guide wire was obtained in the same manner as in example 5, except that the quinacridone organic pigment was not blended in the preparation of the coating liquid for forming the first layer.

The guide wires obtained in examples 1 to 5 and comparative examples 1 to 2 were evaluated for visibility on the curtain, visibility with guide wires of other colors, and peeling resistance of the coating layer by the following methods. The results are shown in table 1 below.

(evaluation method: visibility)

The guide wires obtained in examples and comparative examples were arranged on a blue surgical drape (trade name: Solution Pack, manufactured by Terumo Corporation), and visibility on the drape was confirmed.

O: can be visually recognized on the curtain

X: it is difficult to visually recognize the screen.

(evaluation method: discrimination with other colored guide wire)

The guide wires obtained in examples and comparative examples, and blue guide wires (trade name: Runthrough NS, manufactured by Terumo Corporation), green guide wires (trade name: high-TORQUE BALANCE MIDDLEWEIGHT, manufactured by Abbott Corporation) and white guide wires (trade name: PT2, manufactured by Boston Scientific Corporation) were arranged on a blue surgical drape (trade name: Solution Pack, manufactured by Terumo Corporation), and the visibility with the blue, green and white guide wires was visually confirmed.

Very good: unambiguous identification with respect to blue, green and white guide wires

O: identification with respect to blue, green, and white guidewires

X: difficult to identify relative to blue, green, and white guidewires.

(evaluation method: Peel resistance)

The guide wires obtained in examples 1 to 5 and comparative examples 1 to 2 were tightened under a condition of 10N · cm by a torquer (manufactured by RADIFOCUS Torque Device, Terumo Corporation), and the torquer was rotated 10 turns while the guide wire was fixed. Then, the presence or absence of coating peeling (peeling resistance) was confirmed.

Very good: no peeling was observed visually (no change under microscope)

O: no peeling was observed visually (damage was observed under a microscope)

X: peeling was visually observed.

When the peeling resistance is "excellent" or "o", the coating layer has excellent adhesion (adhesion between the first layer and the second layer, and adhesion between the first layer and the elongated body) and good strength.

[ Table 1]

(Table 1)

As shown in table 1, the guide wires (examples 1 to 5) having a coating layer using both an organic pigment and titanium oxide had high visibility on a blue nonwoven fabric (curtain), and also had excellent visibility with guide wires of other colors (blue, green, and white), and also had excellent adhesion and strength of the coating layer. When the content of titanium oxide is equal to or more than the content of the organic pigment, the adhesion and strength of the coating layer are further improved.

On the other hand, the guidewires having a coating layer in which an organic pigment and titanium oxide were not used together (comparative examples 1 and 2) were inferior in visibility to guidewires of other colors (blue, green, and white). Further, according to comparative example 1, since the peeling resistance of the coating layer not using titanium oxide is low, it is estimated that at least one of the adhesion and the strength is insufficient.

(example 6)

A guidewire was obtained in the same manner as in example 4, except that the amount of DISPERBYK-2055 added as a dispersant was changed to 1.5g (3.8 wt% for organic pigment and titanium oxide and 1.8 wt% for solid content) in the preparation of the coating liquid for forming the first layer.

(example 7)

A guidewire was obtained in the same manner as in example 4, except that the amount of DISPERBYK-2055 added as a dispersant was changed to 1.9g (4.8 wt% for organic pigment and titanium oxide and 2.2 wt% for solid content) in the preparation of the coating liquid for forming the first layer.

(example 8)

A guidewire was obtained in the same manner as in example 4, except that the amount of DISPERBYK-2055 added as a dispersant was changed to 4.8g (12.0 wt% for organic pigment and titanium oxide and 5.4 wt% for solid content) in the preparation of the coating liquid for forming the first layer.

(example 9)

A guidewire was obtained in the same manner as in example 4, except that the amount of DISPERBYK-2055 added as a dispersant was changed to 10.0g (25.0 wt% for organic pigment and titanium oxide and 10.7 wt% for solid content) in the preparation of the coating liquid for forming the first layer.

(example 10)

A guidewire was obtained in the same manner as in example 4, except that the amount of DISPERBYK-2055 added as a dispersant was changed to 28.8g (72.0 wt% for organic pigment and titanium oxide and 25.6 wt% for solid content) in the preparation of the coating liquid for forming the first layer.

As described above, the visibility on the curtain, the visibility with guide wires of other colors (blue, green, and white), and the peeling resistance (adhesion and strength) of the coating were evaluated. The results are shown in table 2 below.

[ Table 2]

(Table 2)

As shown in table 2, the guide wires obtained in examples 6 to 10 were all highly visible on a blue nonwoven fabric (curtain), and were excellent in visibility with guide wires of other colors (blue, green, and white), and were excellent in adhesion and strength of the coating layer.

It should be noted that the present application is based on japanese patent application No. 2017-067868 filed on 3, 30, 2017, the disclosure of which is incorporated herein by reference in its entirety.

Description of the reference numerals

100 guide wires,

110 core part,

110a core part, a tip end part of the core part,

111a first core part,

111a flat plate part,

111b a tapered part,

111c a constant outer diameter portion,

112 second core part,

113 a joint part,

130 coil parts (medical coils),

130a first coil portion,

130b a second coil part,

140 wires, a,

151 first layer,

152 a second layer,

181 a first fixing part,

182 a second fixing part,

183 a third fixing part,

191 a resin layer,

192 resin layer,

193 a resin layer,

194 a resin layer.

Claims

1. A medical device comprising an elongated body and a resin layer covering at least a proximal end portion of the elongated body, wherein,

the resin layer has: a first layer containing a first fluororesin, an organic pigment and titanium oxide; and a second layer formed over the first layer and comprising a second fluorine resin,

wherein the content of the titanium oxide is 100 to 400 wt% based on 100 wt% of the content of the organic pigment,

the organic pigment includes at least one selected from the group consisting of azo pigments, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, perylene pigments, and diketopyrrolopyrrole pigments.

2. The medical device according to claim 1, wherein a content of the organic pigment in the first layer is 5% by weight or more with respect to a content of the first fluororesin.

3. The medical device according to claim 1 or 2, wherein the first layer further contains a dispersant, and the content of the dispersant is 80% by weight or less with respect to 100% by weight of the total content of the organic pigment and the titanium oxide.

4. The medical device according to claim 1 or 2, wherein the first fluororesin contains at least one selected from the group consisting of Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (PETFE).

5. The medical device according to claim 1 or 2, wherein the thickness of the first layer is 0.8 to 100 μm.

6. The medical device according to claim 1 or 2, wherein the thickness of the resin layer is 1 to 200 μm.

7. The medical device according to claim 1 or 2, wherein the total content of the organic pigment and the titanium oxide in the second layer is less than 5% by weight based on the solid content of the second layer.

8. The medical device of claim 1 or 2, wherein the medical device is a guidewire.

9. The medical device according to claim 8, wherein the resin layer is provided between a position 300mm away from the distal end of the guide wire toward the proximal end side and the proximal end of the guide wire.

10. The medical device according to claim 8, wherein the resin layer is provided between a position 300mm away from the distal end of the guide wire toward the proximal end side and a position 3500mm away from the distal end of the guide wire toward the proximal end side.

11. The method for manufacturing a medical device according to any one of claims 1 to 10, comprising:

coating a coating liquid containing a first fluororesin, an organic pigment and titanium oxide on at least a proximal end portion of the elongated body to form a first coating film,

a second coating film is formed by applying a coating liquid containing a second fluorine resin on the first coating film, and then the second coating film is fired at a temperature equal to or higher than the melting points of the first fluorine resin and the second fluorine resin,

wherein the content of the titanium oxide is 100% by weight or more and 400% by weight or less with respect to 100% by weight of the content of the organic pigment.